Manufacture of new indophenolic compounds and of dyestuffs therefrom.



- applied. To this acid.

i. nan.

EDWARD WRAY, 0F FAIIRFIEELB, N'Elilt I/IAIICHESTEE, ENGL I (3 0.,LIMITED, CLAYTUIG', IVIADTCHESCLER,

MANUFACTURE 0Z5 ll'EW' INIJOPHENOLXC CUTtL'PUUNDEfi Specification oi.Letters AND 035' L2dilstd5.

No Drawing. hpplieation filed August .2, 191*.5. Serial To all whom itconcern:

Be it known that I, EDWARD What, a subject of the King of Great.Britain, r siding at Manchester road, Fairfield, near Liam Chester,England, have invented a Av and useful Manufacture of New lfnd hcnolicCompounds and of Dyestuffs Thereiroin, of which the following is aspecification.

I have found that carbazyl l -1C6tl6 acid, 01' esters thereof, which canbe obtained by condensing thereof, with chlor-acetic acid, or an esterthereof can be converted into indophenols by condensation (in sulfuricacid) with para-nitroso-phenol, or a homologue, or de rivative thereof,and that if these indophenols, or their leuco-coinpounds, be treatedwith sulfurizing agents, valuable dyestufis are produced, which can heused for yeing in the presence of alkaline sulfide, or as vat dyes, thedyeings being very fast against washing, light and bleaching. 1

The following are examples of how this invention may be performed, but Ido not limit myself to these examples. The parts are by Weight.

Ewampleof the production of an z'udopiw colic compozmal.

41 parts of para-nitroso-phenol are dissolved in about 410 parts ofconcentrated sulfuric acid to which external cooling is solution partsof carbazyl-N-acetic acid dissolved in about 750 parts of coldconcentrated sulfuric gClCl, are added, while stirring and cooling well,When the reaction is complete the whole is" poured onto ice and ofcondensation is filtered oiit and washed with Water until it is freefrom mineral acid. x

In the dry state the indophenol is a darlr blue powder which isinsoluble in water, or in dilute acids, but is soluble in concentrated.sulfuric acid, the solution being green and is also soluble in dilutecarbonate of soda, the solution being bluish violet.

In the same manner corresponding iudophenols (which, however, are notdilute carbonate or". soda) can from the esters oi? the c,

For the production of the carhazole, or an alkaline salt the separatedproduct tl il mii Example 0 production, of o: dlucstttfi ci ye 6% partsof sulfur and M0 parts oi tallized sodium sulhd are melted to until thesuli. is compl ieiy o e parts oi: Wa or are addei nil a of theindopheuol as obtai the preceding eruunple, (or pound thereof) in.

The solution is then evapora boiling point of the nun-3s has risen. tolie centigrade at which temperature boiling is on continued for abouthours with a reflux condenser. The melt is then diluted with Water andpurified by blowingir throu jyh the mass until thewhole is oxidi ed. litis then filtered from the precipitated sul" 11? an d the coloring matterthrown out from the .Cl"""ate by the addition oi. acid. Ur the dilutedmelt can be completely precipitated by the addition of acid and theleu'co coloring matter be dissolved out by the addition oi: soda andfiltered from the residue oi? sulfur, and precipitating by acid or othersuitable means.

The coloring matter, and also itsleuco body, are characterized by theirsolubility in sodium carbonate solution, -from which solution they canbe precipitated by means of an organic, or mineral, acid.

in the dry state the dyestufi" is black powder havii'ig; a metallicluster and is insoluble in Water and in dilute acids i it I I soluble inconcentrated sult'u l lution heir trot L131",

a hluish- It dyes cotton, from a hydrosulfite vat, or from a sodiumsulfid bath, a bright blue.

By melting, according to the same method the indophenols resulting fromthe esters o carbaZyl-N-acetic acid dyestuffs of similar properties canbe obtained.

In the following claims in the expression para-nitroso phenol, I includepara-nitroso-phenol itself and homologues, and derivatives thereof; inthe expression ,carbaZyl-N-acetic acid I include also the estersthereof; and in the expression indophenolic compound I include also theleuco compound.

What I claim is 1. The manufacture of indophenolic com- "pounds bycondensing earba-zyl-N'acetic acid with para-nitroso-phenol.

, diluting the melt with ing carbazyl-N-acetic 2. The manufacture of anindophenolic compound by dissolving para-nitroso-phenol in concentratedsulfuric acid While applying ing together sulfur and crystallized sodiumsu fi d, adding water and stirring in an indophenolic compound, preparedby condensphenol, evaporating, continuing boiling, water and separatingthe coloring matter by blowing air through the mass, filtering outtating by means of acid.

6. The manufacture of a leuco dyestuf'f by melting together sulfur andcrystallized sodium sulfid', adding water and stirring in anindophenolic compound, evaporating, continuing boiling and diluting'themelt with water, precipitating by means of acid and dlssolving out theleuco compound by the acid with para-nitroso the sulfurand'precipinarrate addition of soda, filtering from sulfur, andprecipitating.

7. As new articles of manufacture indophenolic compounds which have beenmade by condensing carbazyLN-acetic acid with para-nitroso-phenol 8. Asa new article of manufacture an indophenolic compound which has beenmade by dissolving para-nitroso-phenol in concentrated sulfuric acidwhile applying external cooling and, then,'while stirring and cooling,adding to this solution carbazyl-N- acetic acid dissolved in coldconcentrated sulfuric acid and pouring onto ice, filtering off the ingit.

9. As new articles of manufacture dyestuffs which have been made bycondensing cai'bazyl-N-acetic acid with para-nitrcse phenol, and thenheating the resulting indophenolic compound with a sulfurizing agent.

10. As new articles of manufacture, dyestuffs which have been made bycondensing carbazyl-N-acetic acid with. para-nitroso phenol, and thenheating; the resulting indophenolic compound with alkaline polysulfid.

llh'yAs a new article of manufacture, a dyestutl' which has been made bymelting together sulfur and crystallized sodium sulfid, adding water andstirring in an indophenolic compound prepared by condensingcarbazyl-N-acetic acid with para-nitroso phenol, evaporating, continuingboiling, diluting the meltwith Water and separating the coloring matterby blowing air through the mass, filtering out the sulfur andprecipitating by means of acid.

12. As a new article of manufacture a leuco dyestufi'whieh has been madeby melting together sulfur and'erystallized sodium sulfid, adding waterand stirring in an indophenolic compound, evaporating, continuingboiling and diluting the melt with water, precipitating by means of acidand dissolving out the leuco compound by the addition of soda, filteringfrom sulfur, and precipi- .tating.

In testimony whereof I have signed my name to this specification in thepresence of two subscribing witnesses.

EDWARD wnAY. l/Vitnesses Ewan) SIMPSON Mosnnnr, MARION E, CLOUD.

product of cbndensation and wash-

